All elementary steps of a chemical reaction have been successfully induced on individual molecules with a scanning tunneling microscope (STM) in a controlled step-by-step manner utilizing a variety of manipulation techniques. The reaction steps involve the separation of iodine from iodobenzene by using tunneling electrons, bringing together two resultant phenyls mechanically by lateral manipulation and, finally, their chemical association to form a biphenyl molecule mediated by excitation with tunneling electrons. The procedures presented here constitute an important step towards the assembly of individual molecules out of simple building blocks in situ on the atomic scale.

Two conformations of isolated single TBrPP-Co molecules on a Cu(111) surface are switched by applying +2.2 V voltage pulses from a scanning tunneling microscope tip at 4.6 K. The TBrPP-Co has a spin-active cobalt atom caged at its center, and the interaction between the spin of this cobalt atom and free electrons from the Cu(111) substrate can cause a Kondo resonance. Tunneling spectroscopy data reveal that switching from the saddle to a planar molecular conformation enhances spin-electron coupling, which increases the associated Kondo temperature from 130 to 170 K. This result demonstrates that the Kondo temperature can be manipulated just by changing molecular conformation without altering chemical composition of the molecule.

The design of artificial molecular machines often takes inspiration from macroscopic machines. However, the parallels between the two systems are often only superficial, because most molecular machines are governed by quantum processes. Previously, rotary molecular motors powered by light and chemical energy have been developed. In electrically driven motors, tunnelling electrons from the tip of a scanning tunnelling microscope have been used to drive the rotation of a simple rotor in a single direction and to move a four-wheeled molecule across a surface. Here, we show that a stand-alone molecular motor adsorbed on a gold surface can be made to rotate in a clockwise or anticlockwise direction by selective inelastic electron tunnelling through different subunits of the motor. Our motor is composed of a tripodal stator for vertical positioning, a five-arm rotor for controlled rotations, and a ruthenium atomic ball bearing connecting the static and rotational parts. The directional rotation arises from sawtooth-like rotational potentials, which are solely determined by the internal molecular structure and are independent of the surface adsorption site.

Mathematics and art converge in the fractal forms that also abound in nature. We used molecular self-assembly to create a synthetic, nanometer-scale, Sierpinski hexagonal gasket. This nondendritic, perfectly self-similar fractal macromolecule is composed of bis-terpyridine building blocks that are bound together by coordination to 36 Ru and 6 Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

We report manipulation of a Kondo resonance originated from the spin-electron interactions between a twodimensional molecular assembly of TBrPP-Co molecules and a Cu(111) surface at 4.6 K using a low temperature scanning tunneling microscope. By manipulating nearest-neighbor molecules with a scanning tunneling microscope tip we are able to tune the spin-electron coupling of the center molecule inside a small hexagonal molecular assembly in a controlled step-by-step manner. The Kondo temperature increases from 105 to 170 K with a decreasing the number of nearest neighbor molecules from six to zero. This Kondo temperature variation is originated from the scattering of surface electrons by the molecules located at the edges of the molecular layer, which reduces spinelectron coupling strength for the molecules inside the layer. Investigations on different molecular arrangements indicate that the observed Kondo resonance is independent on the molecular lattice.